Novel azolyl-aroxymethyl-dimethylpentinol fungicides

ABSTRACT

Novel fungicidally active compounds of the formula ##STR1## in which X is nitrogen or the CH group, 
     Y is hydrogen, bromine or iodine, 
     Z is oxygen, sulphur, the --SO-- group or the --SO 2  -- group, and 
     Ar is optionally substituted aryl, 
     or physiologically tolerated addition products thereof with acids or metal salts.

This is a division of application Ser. No. 816,540, filed Jan. 6, 1986,now U.S. Pat. No. 4,758,582.

The present invention relates to novelazolyl-aroxymethyl-dimethylpentinols, to a process for their preparationand to their use as fungicides.

It has already been disclosed that substituted 1-hydroxyalkyl-azolylderivatives possess fungicidal properties (compare, for example, EP-A0,084,834. The action of these compounds is however not always fullysatisfactory, especially when low concentrations are used.

There have now been found the new azolyl-aroxymethyl-dimethylpentinolsof the general formula (I) ##STR2## in which X represents nitrogen andthe CH group,

Y represents hydrogen, bromine and iodine,

Z represents oxygen, sulphur, the --SO-- group and the --SO₂ -- groupand

Ar represents optionally substituted aryl,

and their physiologically tolerated acid addition salts and metal saltcomplexes.

The azolyl-aroxymethyl-dimethylpentinols of the formula (I) ##STR3## inwhich X represents nitrogen and the CH group,

Y represents hydrogen, bromine and iodine,

Z represents oxygen, sulphur, the --SO-- group and the --SO₂ -- groupand

Ar represents optionally substituted aryl,

and their physiologically tolerated acid addition salts and metal saltcomplexes, are obtained when oxirane derivatives of the formula (II) inwhich Z and Ar have the abovementioned meaning are reacted with azolesof the formula (III) ##STR4## in which Z and Ar h ave the abovementionedmeaning are reacted with azoles of the formula (III) ##STR5## in which Xhas the abovementioned means if appropriate in the presence of a diluentand of a base and, if appropriate, the thus obtained compounds of theformula (Ia) (namely those compounds of the general formula (I) in whichY represents hydrogen) ##STR6## in which X, Z and Ar have theabovementioned meaning, are halogenated with bromine or iodine, ifappropriate in the presence of a diluent and of an acid acceptor, andfurthermore, if appropriate, the resulting compounds of the generalformula (I) are subjected to an addition reaction with an acid or ametal salt.

The new azolyl-aroxymethyl-dimethylpentinols of the formula (I) exhibitpowerful fungicidal properties. Surprisingly, the compounds according tothe invention show a substantially more powerful fungicidal action thanthe 1-hydroxyalkyl-azolyl derivatives known from the state of the art.Accordingly, the new compounds constitute an enrichment of the state ofthe art.

Preferred compounds accordign to the invention, of the formula (I), arethose

in which

Ar represents phenyl and naphthyl, it being possible for the saidradicals to be substituted by halogen, by alkyl, alkoxy and alkylthioeach with up to 4 carbon atoms, by halogenoalkyl, halogenoalkoxy andhalogenoalkylthio each with up to 2 carbon atoms and up to 5 halogenatoms, by optionally halogen-substituted phenyl or phenoxy and, finally,by the groups CH₃ --O--N═CH-- and CH₃ --O--N═C(CH₃)--, and

X, Y and Z have the meaning given in the definition of the invention.

Particularly preferred compounds of the general formula (I) are those

in which

Ar represents phenyl which is optionally monosubstituted, disubstitutedor trisubstituted by fluorine and chlorine, by methyl, ethyl andisopropyl, by halogenomethyl with 1 to 3 fluorine or chlorine atoms, bymethoxy, methylthio, trifluoromethoxy and trifluoromethylthio and/or bythe groups CH₃ --O--N═CH--and CH₃ --O--N═C(CH₃)-- as well asmonosubstituted by phenyl or phenoxy, the two last-mentioned radicals,in turn, being optionally monosubstituted, disubstituted ortrisubstituted by fluorine and chlorine, and

X, Y and Z have the meaning given in the definition of the invention.

Specifically, the following compounds of the general formula (I) may bementioned as examples, in addition to the compounds mentioned in thepreparation examples:

    ______________________________________                                        X      Y       Z      Ar                                                      ______________________________________                                        CH     H       O                                                                                     ##STR7##                                               CH     I       O                                                                                     ##STR8##                                               CH     H       O                                                                                     ##STR9##                                               CH     I       O                                                                                     ##STR10##                                              CH     H       O                                                                                     ##STR11##                                              CH     I       O                                                                                     ##STR12##                                              CH     Br      O                                                                                     ##STR13##                                              CH     H       O                                                                                     ##STR14##                                              CH     I       O                                                                                     ##STR15##                                              CH     H       S                                                                                     ##STR16##                                              CH     I       S                                                                                     ##STR17##                                              N      H       S                                                                                     ##STR18##                                              N      I       S                                                                                     ##STR19##                                              N      H       S                                                                                     ##STR20##                                              N      I       S                                                                                     ##STR21##                                              N      H       SO                                                                                    ##STR22##                                              N      H       SO.sub.2                                                                              ##STR23##                                              N      I       SO.sub.2                                                                              ##STR24##                                              N      I       O                                                                                     ##STR25##                                              N      Br      O                                                                                     ##STR26##                                              N      Br      O                                                                                     ##STR27##                                              N      I       O                                                                                     ##STR28##                                              N      H       O                                                                                     ##STR29##                                              N      I       O                                                                                     ##STR30##                                              N      H       O                                                                                     ##STR31##                                              N      I       O                                                                                     ##STR32##                                              N      H       O                                                                                     ##STR33##                                              N      H       O                                                                                     ##STR34##                                              N      I       O                                                                                     ##STR35##                                              N      H       O                                                                                     ##STR36##                                              N      H       O                                                                                     ##STR37##                                              N      H       O                                                                                     ##STR38##                                              ______________________________________                                    

If, for example,2-(4-chlorophenoxymethyl)-2-(3-methyl-1-butin-3-yl)-oxirane and1,2,4-triazole are used as starting materials, in the presence of sodiumbutanolate, for the preparation of the compounds according to theinvention, of the formula (I), the course of the reaction can berepresented by the following equation: ##STR39##

If, the compound thus obtained is halogenated, for example with iodinein the presence of sodium hydroxide solution, then this can berepresented as follows: ##STR40##

The oxirane derivatives to be used as starting materials are defined bythe general formula (II). In this formula, Z and Ar preferably have themeanings which have already been mentioned as preferred for thesesubstituents when discussing the compounds of the formula (I).

The oxirane derivatives of the formula (II) can be prepared inaccordance with generally known methods (see, in this context, EP-A0,084,835. Thus, for example, the corresponding ketones of the formula(IV) ##STR41## in which Z and Ar have the abovementioned meaning, caneither (a) be reacted with dimethyloxosulphonium methylide in thepresence of a suitable diluent, such as, for example,dimethylsulphoxide, in the temperature range between +20° and 80° C., or(b) be reacted with trimethylsulphonium methyl-sulphate in the presenceof an inert organic solvent, such as, for example, acetonitrile, and inthe presence of a base, such as, for example, sodium methylate, in thetemperature range between 0° and 60° C. (compare, in this context, thecited EP-A and the data in J. Amer. Chem. Soc. 87, pages 1363-1364(1965), which include further details).

The ketones of the formula (IV) are also obtained in a known manner, byreacting 1-chloro-3,3-dimethyl-4-pentin-2-one of the formula (V)##STR42## with phenols or thiophenols in the presence of an acidacceptor, such as potassium carbonate, and a diluent, such as acetone,in the temperature range between +40° and 100° C. (the known Williamsonether synthesis). The compounds thus obtained, of the formula (VI)##STR43## in which Z' represents oxygen or sulphur and

Ar has the meanings given above,

can, in the case of the sulphur compounds, be further converted to thesulphoxide and sulphone stages. This is done in a generally customarymanner and the oxidation is carried out with, for example, benzoylperoxide or hydrogen peroxide or with potassium permanganate (the latteronly or the sulphone stage).

The formula (III) provides an unambiguous definition of the azolesadditionally needed to prepare the compounds according to the invention,of the formula (I). The compounds imidazole and 1,2,4-triazole, embracedby this formula, are generally known compounds customary inlaboratories.

Possible diluents for use in the preparation of the compounds accordingto the invention are inert organic solvents. These preferably includealcohols, such as methanol, ethanol, isopropanol or butanol, as well asnitriles, such as acetonitrile, and also ethers, such as tetrahydrofuranor dioxane and, finally, dimethylformamide.

The preparation of the compounds according to the invention ispreferably carried out in the presence of bases. For this purpose, allcustomarily usable inorganic and organic bases may be employed. Thesepreferentially include alkali metal carbonates, such as, for example,sodium carbonate and potassium carbonate, alkali metal hydroxides, suchas, for example, sodium hydroxide, alkali metal alcoholates, such as,for example, sodium methylate, ethylate and butylate and potassiummethylate, ethylate and butylate, alkali metal hydrides, such as, forexample, sodium hydride and, finally, tertiary amines, such astriethylamine.

In carrying out the preparation, the reaction temperatures can be variedwithin a substantial range. In general, the reaction is carried out atbetween +40° and 180° C., preferably between 60° and 150° C.

In carrying out the process of preparation, it is preferred to employ 1to 2 moles of azole of the formula (III) and, where appropriate, up to1.5 moles of base per mole of oxirane of the formula (II). The endproducts are isolated in a generally customary manner.

The compounds of the formula (I) obtainable by the process according tothe invention can be converted to acid addition salts or metal complexsalts in a customary manner (in this context, compare also the data inEP-A 0,084,834, already cited).

Preferably, the following acids may be employed to preparephysiologically tolerated acid addition salts of the compounds of theformula (I): the hydrogen halide acids, such as, for example,hydrochloric acid and hydrobromic acid, especially hydrochloric acid, aswell as phosphoric acid, nitric acid, sulphuric acid, monofunctional andbifunctional carboxylic acids and hydroxycarboxylic acids, such as, forexample, acetic acid, maleic acid, succinic acid, fumaric acid, tartaricacid, citric acid, salicylic acid, sorbic acid and lactic acid, as wellas sulphonic acids, such as, for example, p-toluenesulphonic acid and1,5-naphthalenedisulphonic acid.

Preferably, salts of metals of main groups II to IV and of sub-groups I,II and IV to VIII of the periodic table, with copper, tin, iron andnickel being mentioned as examples, may be used to prepare metal saltcomplexes of the compounds of the formula (I). Suitable anions of thesalts are those preferentially derived from the following acids:hydrogen halide acid, such as, for example, hydrochloric acid andhydrobromic acid, as well as phosphoric acid, nitric acid and sulphuricacid.

The active compounds according to the invention exhibit a powerfulmicrobicidal action and can be employed in practice for combatingundesired microorganisms. The active compounds are suitable for use asplant protection agents.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal and bacterial diseases included underthe abovementioned main headings are mentioned below as non-limitingexamples:

Uromyces species, such as, for example, Uromyces appendiculatus;Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;Venturia species, such as, for example, Venturia inaequalis; Podosphaeraspecies, such as, for example, Podosphaera leucotricha; Phytophthoraspecies, such as, for example, Phytophthora infestans; Erysiphe species,such as, for example, Erysiphe graminis; Puccinia species, such as, forexample, Puccinia recondita; Drechslera species, such as, for example,Drechslera graminea (synonym: Helminthosporium); Fusarium species, suchas, for example, Fusarium culmorum; Ustilago species, such as, forexample, Ustilago nuda or Ustilago avenae; Septoria species, such as,for example, Septoria nodorum; Tilletia species, such as, for example,Tilletia caries; Xanthomonas species, such as, for example, Xanthomonasoryzae; Pseudomonas species, such as, for example, Pseudomonaslachrymans; Pyricularia species, such as, for example, Pyriculariaoryzae; Pellicularia species, such as, for example, Pelliculariasasakii, and Pyrenophora species, such as, for example, Pyrenophorateres (conidia form: Drechslera, synonym: Helminthosporium,Leptosphaeria species, such as, for example, Leptosphaeria nodorum;Cochliobolus species, such as, for example, Cochliobolus sativus,(conidia form: Drechslera, synonym: Helminthosporium); and Cercosporaspecies, such as, for example, Cercospora canescens.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

The compounds are, in particular, effective against Cochliobolus sativuson barley, Fusarium culmorum on wheat, Venturia in apple cultures andPyricularia in rice cultures. In addition, there should be mentioned abroad action as a spray and seed dressing against cereal diseases suchas mildew, rust, Pseudocercosporella herpotrichoides, Pyrenophora teres,Drechslera graminea and Fusarium nivale.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, suspensions, powders, foams, pastes,granules, aerosols, natural and synthetic materials impregnated withactive compound, very fine capsules in polymeric substances and incoating compositions, for use on seed, and formulations used withburning equipment, such as fumigating cartridges, fumigating cans,fumigating coils and the like, as well as ULV cold mist and warm mistformulations.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide; as solid carriers: for example ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such ashighly-dispersed silicic acid, alumina and silicates; as solid carriersfor granules: for example crushed and fractionated natural rocks such ascalcite, marble, pumice, sepiolite and dolomite, as well as syntheticgranules of inorganic and organic meals, and granules of organicmaterial such as sawdust, coconut shells, corn cobs and tobacco stalks;as emulsifying and/or foam-forming agents: for example, non-ionic andanionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products; as dispersing agents: for examplelignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Mineral and vegetableoils are further possible additives.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin, azo and metal phthalocyanine dyestuffs, and tracenutrients such as salts or iron, manganese, boron, copper, cobalt,molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations or in the various use forms as a mixture with other knownactive compounds, such as fungicides, bactericides, insecticides,acaricides, nematicides, herbicides, bird repellents, growth factors,plant nutrients and agents for improving soil structure.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom by further dilution,such as ready-to-use solutions, emulsions, suspensions, powders, pastesand granules. They are used in the customary manner, for example bywatering, immersion, spraying, atomizing, misting, vaporizing,injecting, slurrying, brushing on, dusting, scattering, dry dressing,moist dressing, wet dressing, slurry dressing or encrusting.

When used to treat parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001% by weight.

In the treatment of seeds, amounts of active compound of 0.001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, amounts of active compound of 0.00001 to 0.1%by weight, preferably 0.0001 to 0.02% by weight, are required at theplace of action.

PREPARATION EXAMPLES Example 1 ##STR44##

133 g (0.53 mole) of crude2-(4-chlorophenoxymethyl)-2-(3-methyl-but-1-in-3-yl)-oxirane, dissolvedin 100 ml of n-butanol, are added dropwise, with stirring, to a boilingsolution of 5 g (0.052 mole) of sodium butanolate and 133 g (0.583 mole)of 1,2,4-triazole in 300 ml of n-butanol. The solution is heated to theboil for nine hours. The solvent is then distilled off in vacuo and theoily residue which remains is taken up in 500 ml of methylene chloride.The solution is washed three times with 1,000 ml of water at a time, andthe organic phase is dried over sodium sulphate and then evaporated invacuo. The oil which remains (150 g) is filtered over silica gel, withchloroform as the eluant. This gives 101 g (0.31 mole, that is to say58.5% of theory) of2-(4-chlorophenoxymethyl)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-pent-4-in-2-olas colorless crystals of melting point 89°-91° C.

In addition, by use of ethyl acetate as eluant, 20.6 g (that is to say11.9% of theory) of2-(4-chlorophenoxymethyl)-3,3-dimethyl-1-(1,2,4-triazol-are obtained ascolorless crystals of melting point 136°-137° C.

Intermediate 1 ##STR45##

114.5 ml (1.2 moles) of dimethyl sulphate are added dropwise at between20° and 30° C. to a solution of 56.9 ml (1.32 moles) of dimethylsulphide in 200 ml of tert.-butanol. After 12 hours, 149 g (0.6 mole) of1-(4-chlorophenoxy)-3,3-dimethyl-pent-4-in-2-one are added, and 134.4 g(2.4 moles) of potassium hydroxide powder are then introduced a littleat a time. The mixture is left to stand for 10 hours at room temperatureand 1,000 ml of water and 400 ml of toluene are then added. The organicphase is separated off, the aqueous phase is extracted twice with 200 mlof toluene at a time, and the combine toluene phases are washed threetimes with 1,000 ml of water at a time, dried over sodium sulphate andevaporated in vacuo. 149 g (that is to say 99% of theory) of crude2-(4-chlorophenoxymethyl)-2-(3-methyl-but-1-in-3-yl)-oxirane remain as abrownish viscous oil which can be reacted further without additionalpurification.

Intermediate 2 ##STR46##

A solution of 98 g (0.67 mole) of 1-chloro-3,3-dimethyl-pent-4-in-2-oneis added dropwise, with stirring, to a boiling mixture of 86.1 g (0.67mole) of 4-chlorophenol and 92.5 g (o.67 mole) of potassium carbonatepowder in 500 ml of acetone. After five hours the mixture is filtered,the filtrate is evaporated, the residue is taken up in 250 ml ofmethylene chloride and this solution is washed with 200 ml of 1N sodiumhydroxide solution and 200 ml of water. After the solvent has beendistilled off, 149 g (that is to say 94% of theory) of1-(4-chlorophenoxy)-3,3-dimethyl-pent-4-in-2-one are obtained as acolorless viscous oil, which upon standing solidifies to crystals.

Intermediate 3 ##STR47##

275 g (1.25 moles) of 1-chloro-3,3-dimethyl-2-phenoxy-pent-1-en-4-ine in1.25 liters of ethanol and 620 ml of concentrated hydrochloric acid areheated for 5 hours under reflux. The mixture is diluted with water andrepeatedly extracted with n-hexane. After drying the extracts andstripping off the solvent, 176 g of crude product remain. Distillationgives 149.9 (that is to say 83% of theory) of1-chloro-3,3-dimethyl-pent-4-in-2-one of boiling point 67°-70° C./20 mmHg.

NMR (CDCL₃): 1.45 (s, 6H); 2.5 (s, 1H); 4.75 (s, 2H).

Intermediate 4 ##STR48##

Method A:

23.2 g (0.2 mole) of sodium phenolate and 12.65 g (0.1 mole) of1-chloro-3,3-dimethyl-penta-1,4-diine in 100 ml of absoluteN,N-dimethylformamide are heated under reflux for 7 hours. The mixtureis diluted with water and is repeatedly extracted with methylenechloride, and the extract is washed with dilute sodium hydroxidesolution. After dry8ing, and stripping off the solvent, 16.4 g (that isto say 74% of theory) of1-chloro-3,3-dimethyl-2-phenoxy-pent-1-en-4-ine, of boiling point85°-95°°C./0.1 mm Hg, are obtained.

NMR (CDCL₃): 1.45 (s, 6H); 2.3 (s, 1H); 6.45 (s, 1H); 6.7-7.5 (m, 5H).

Method B:

163 g (1 mole) of 1,5-dichloro-3,3-dimethyl-pent-1-en-4-ine and 232 g (2moles) of sodium phenolate in 1 liter of absolute N,N-dimethylformamideare heated to 140° C. in the course of 3 hours and stirring is thencontinued for 4 hours. The mixture is worked up as described for methodA, givign 204 g of crude product, which after distillation (boilingpoint 0.15/87°-94° C.) gives 141 g (that is to say 64% of theory) of1-chloro-3,3-dimethyl-2-phenoxy-pent-1-en-4-ine.

Intermediates 5 and 6 ##STR49##

A solution of 800 g (20 moles) of NaOH in 200 ml of water is heated to100° C. 472 g (2 moles) of 1,1,5,5-tetrachloro-3,3-dimethyl-pent-1-eneand a solution of 5 g of tetrabutylammonium bromide in 3 ml of water areadded with stirring. A further four amounts of 5 g of tetrabutylammoniumbromide dissolved in 3 ml of water are added at intervals of 4 hours.After 20 hours, the reaction product is isolated from the reactionmixture by steam distillation. The non-aqueous distillate and the waterphase are separated and the reaction products are then isolated in apure form by fractional distillation in vacuo, using a column. Thisgives 12.9 g (4% of theory) of 1,5-dichloro-3,3-dimethyl-pent-1-en-4-ineof boiling point 20° C./18 mm Hg and 233 g (that is to say 92% oftheory) of 1-chloro-3,3-dimethyl-penta-1,4-diine of boiling point50°-52° C./18 mm Hg.

Example 2 ##STR50##

3.8 g (0.015 mole) of iodine and 7.2 ml (containing 0.072 mole of sodiumhydroxide) of concentrated caustic soda solution are simultaneouslystirred into a solution of 4.8 g (0.015 mole) of2-(4-chlorophenoxymethyl)-3,3-dimethyl-(1,2,4-triazol)-pent-4-in-2-ol(see Example 1) in 50 ml of methanol, in the temperature range ofbetween 20° and 30° C. After one hour, the reaction mixture is stirredinto 500 ml of water. The batch is extracted with methylene chloride andthe organic phase is washed with water, dried over sodium sulphate andconcentrated in vacuo. The viscous residue is taken up in diethyl etherand petroleum ether is added to the solution until it begins to turncloudy. Trituration gives 4.0 g (that is to say 59.3% of theory) of2-(4-chlorophenoxymethyl)-3,3-dimethyl-5-iodo-1-(1 of melting point108°-109° C.

The following compounds of the general formula (I) ##STR51## areobtained analogously to the description in Examples 1 and 2:

    ______________________________________                                        Ex.                                Physical Properties                        No.   X      Y      Z   Ar         (melting point °C.                  ______________________________________                                         3    N      H      O                                                                                  ##STR52## 144-145                                     4    N      H      O                                                                                  ##STR53## oil                                         5    N      H      O                                                                                  ##STR54## 112-113                                     6    N      H      O                                                                                  ##STR55## 117-118                                     7    N      H      O                                                                                  ##STR56## 79-80                                       8    N      H      O                                                                                  ##STR57## oil                                         9    N      I      O                                                                                  ##STR58## oil                                        10    CH     H      O                                                                                  ##STR59## 97-98                                      11    N      I      O                                                                                  ##STR60## 128-130                                    12    CH     H      O                                                                                  ##STR61## 111-112                                    13    CH     H      O                                                                                  ##STR62## 128-129                                    14    N      H      O                                                                                  ##STR63## 105-106                                    15    CH     H      O                                                                                  ##STR64## 139-140                                    16    N      H      O                                                                                  ##STR65## 133                                        17    CH     H      O                                                                                  ##STR66## Oil                                        18    N      H      O                                                                                  ##STR67## Oil                                        19    CH     I      O                                                                                  ##STR68## Oil                                        20    CH     I      O                                                                                  ##STR69## Oil                                        21    N      I      O                                                                                  ##STR70## 109-110                                    22    CH     I      O                                                                                  ##STR71## Oil                                        23    N      I      O                                                                                  ##STR72## Oil                                        24    N      I      O                                                                                  ##STR73## Oil                                        ______________________________________                                    

The following NMR-spectroscopic data characterize those compoundsaccording to the invention, which have been obtained as oils.

(¹ H - NMR); ppm.

Example No. 4

(CDCl₃ ; 60 MHz) 1.45 (s, 6H); 2,3 (s,1H); 3.95 (q,2H); 4.1 (s,1H); 4.68at 6.8 (m, 2H); at 7.4 (m,7H); 7.9 (s,1H); 8.15 (s,1H).

Example No. 8

(CDCl₃ ; 60 MHz) 1.45 (s,6H); 2,2 (s,3H); 2.32 (s,1H); at 3.9 (q,2H); 44.68 (q,2H); 6.5-7.2 (3H;m); 7.9 (s,1H); 8.15 (s,1H).

Example No. 9

(CDCl₃ ; 60 MHz) 1.48 (s,6H), 3.9 (q,2H); 4.1 (s,1H); 4.75 (q,2H);6.6-7.45 (m.3H) 7.9 (s,1H); 8.22 (s,1H).

Example No. 17

(CDCl₃ ; 80 MHz) 1.4 (d,6H); 2.35 (s,1H); at 4.2 (q,2H); 4.2 (br.s,1H);4.9 (s,2H); 6.9-7.7 (m,6H).

Example No. 18

(CDCl₃ ; 80 MHz) 1.45 (d,6H); 2.32 (s,1H); at 4.2 (q,2H); 4.1 (br.s,1H);4.7 (s,2H); 6.8-7.4 (m,3H); 7.9 (s,1H); 8.35 (s,1H).

Example No. 19

(CDCl₃ ; 60 MHz) 1.45 (s,6H); at 3.8 (q,2H); 4.1-4.7 (m,3H); 6.5-7.5(m7H).

Example No. 20

(CDCl₃ ; 60 MHz) 1.45 (s,6H); 3-4.5 (m;5H); 6.65-6.75 (m,7H).

Example No. 22

(CDCl₃ ; 60 MHz) 1.5 (s,6H); at 3.8 (q,2H); 3.6 (br.s,1H); at 4.45(q,2H); 6.7-7.7 (m,6H).

Example No. 23

(CDCl₃ ; 60 MHz) 1.48 (s,6H); at 3.85 (q,2H); 4.1 (s,1H); at 4.75(q,2H); 6.7-7.4 (m,3H); 7.95 (s,1H); 8.2 (s,1H).

Example No. 24

(C Cl₃ ; 60 MHz) 1.45 (d,6H); at 4.25 (q;2H); at 4.1 (m;1H); 4.7 (s;2H);6.85-7.6 (m,3H); 7.95 (s,1H); 8.35 (s,1H).

USE EXAMPLES

The following compounds were employed as comparison substances in theuse examples which follow: ##STR74##

Example A

Cochliobolus sativus test (barley) / protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofCochliobolus sativus. The plants remain in an incubation cabinet for 48hours at 20° C. and 100% relative atmospheric humidity.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compound according to the followingpreparation example: 1.

Example B

Fusarium culmorum test (wheat) / seed treatment

The active compounds are used as dry dressings. These are prepared byextending the particular active compound with a ground mineral to give afinely pulverulent mixture, which ensures uniform distribution on theseed surface.

To apply the dressing, the infected seed is shaken with the dressing ina closed glass flask for 3 minutes.

2 batches of 100 grains of the wheat are sown 1 cm deep in standard soiland are cultivated in a greenhouse at a temperature of about 18° C., inseedboxes which are exposed to light for 15 hours daily.

About 3 weeks after sowing, the plants are evaluated for symptoms.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compounds according to the followingpreparation examples: 3, 4, 5, 2 and 1.

Example C

Venturia test (apple)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous conidiasuspension of the apple scab causative organism (Venturia inaequalis)and then remain in an incubation cabinet at 20° C. and 100% relativeatmospheric humidity for 1 day.

The plants are then placed in a greenhouse at 20° C. and a relativeatmospheric humidity of about 70%.

Evaluation is carried out 12 days after the inoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compounds according to the followingpreparation examples: 1, 3, 4, 5 and 2.

Example D

Pyricularia test (rice)/protective

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier,to the desired concentration.

To test for protective activity, young rice plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous sporesuspension of Pyricularia oryzae. The plants are then placed in agreenhouse at 100% relative atmospheric humidity and 25° C.

Evaluation of the disease infestation is carried out 4 days after theinoculation.

A distinct superiority in activity compared to the prior art is shown inthis text by, for example, the compounds accordign to the followingpreparation examples: 4, 1, 2, 6 and 7.

Example E

Pyricularia test (rice)/systemic

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier,to the desired concentration.

To test for systemic properties, standard soil in which young riceplants have been grown is watered with 40 ml of the preparation ofactive compound. 7 days after this treatment, the plants are inoculatedwith an aqueous spore suspension of Pyricularia oryzae. Thereafter, theplants remain in a greenhouse at a temperature of 25° C. and a relativeatmospheric humidity of 100% until they are evaluated.

Evaluation of the disease infestation is carried out 4 days after theinoculation.

In this test, a clearly superior activity compared with the prior art isshown, for example, by the compounds according to the followingpreparation examples: 1, 5 and 2.

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

We claim:
 1. An azolyl-aroxymethyl-dimethylpentinol of the formula##STR75## in which Y is hydrogen, bromine or iodine,Z is oxygen,sulphur, the --SO-- group or the --SO₂ -- group, and Ar is phenyl ornaphthyl optionally substituted by halogen, alkyl, alkoxy or alkylthioeach with up to 4 carbon atoms, halogenoalkyl, halogenoalkoxy orhalogenoalkylthio each with up to 2 carbon atoms and up to 5 halogenatoms, optionally halogen-substituted phenyl or phenoxy, CH₃ --O--N═CH--or CH₃ --O--N═C(CH₃)--,or a physiologically tolerated addition productthereof with an acid or metal salt.
 2. A compound or addition productaccording to claim 1, in whichAr is phenyl; phenyl independentlysubstituted by up to three radicals selected from the group consistingof fluorine, chlorine, methyl, ethyl, isopropyl. halogenomethyl with 1to 3 fluorine or chlorine atoms, methoxy, methylthio, trifluoromethoxy,trifluoromethylthio, CH₃ --O--N═CH13 or CH₃ --O--N═CH(CH₃)--; or phenylsubstituted by phenyl or phenoxy, the substituents themselves optionallybeing substituted by up to three fluorine or chlorine atoms.
 3. Acompound according to claim 1, wherein such compound is2-(4-fluorophenoxymethyl)-3,3-dimethyl-(imidazol-1-yl)-pent-4-in-2-ol ofthe formula ##STR76## or physiologically tolerated addition productthereof with an acid or metal salt.
 4. A compound according to claim 1,wherein such compound is2-(4-chlorophenoxymethyl)-3,3-dimethyl-1-(imidazol-1-yl)-pent-4-in-2-olof the formula ##STR77## or physiologically tolerated addition productthereof with an acid or metal salt.
 5. A compound according to claim 1,wherein such compound is2-(4-bromophenoxymethyl)-3,3-dimethyl-1-(imidazol-1-yl)-pent-4-in-2-olof the formula ##STR78## or physiologically tolerated addition productthereof with an acid or metal salt.
 6. A compound according to claim 1,wherein such compound is2-(2,5-dichlorophenoxymethyl)-3,3-dimethyl-1-(imidazol-1-yl)-pent-4-in-2-olof the formula ##STR79## or physiologically tolerated addition productthereof with an acid or metal salt.
 7. A compound according to claim 1,wherein such compound is2-(2,6-dichlorophenoxymethyl)-3,3-dimethyl-1-(imidazol-1-yl)-pent-4-in-2-olof the formula ##STR80## or physiologically tolerated addition productthereof with an acid or metal salt.
 8. A compound according to claim 1,wherein such compound is2-(4-chlorophenoxymethyl)-3,3-dimethyl-1-(imidazol-1-yl)-5-iodo-pent-4-in-2-olof the formula ##STR81## or physiologically tolerated addition productthereof with an acid or metal salt.
 9. A compound according to claim 1,wherein such compound is2-(4-bromophenoxymethyl)-3,3-dimethyl-1-(imidazol-1-yl)-5-iodo-pent-4-in-2-olof the formula ##STR82## or physiologically tolerated addition productthereof with an acid or metal salt.
 10. A compound according to claim 1,wherein such compound is2-(2,5-dichlorophenoxymethyl)-3,3-dimethyl-1-(imidazol-1-yl)-5-iodo-pent-4-in-2ofthe formula ##STR83## or physiologically tolerated addition productthereof with an acid or metal salt.
 11. A fungicidal compositioncomprising a fungicidally effective amount of a compound or additionproduct according to claim 1 in admixture with a diluent.
 12. A methodof combating fungi which comprises applying to such fungi or to a fungushabitat a fungicidally effective amount of a compound or additionproduct according to claim
 1. 13. The method according to claim 12,wherein such compoundis2-(4-fluorophenoxymethyl)-3,3-dimethyl-1-(imidazol-1-yl)-pent-4-in-2-ol,2-(4-chlorophenoxymethyl)-3,3-dimethyl-1-(imidazol-1-yl)-pent-4-in-2-ol,2-(4-bromophenoxymethyl)-3,3-dimethyl-1-(imidazol-1-yl)-pent-4-in-2-ol,2-(2,5-dichlorophenoxymethyl)-3,3-dimethyl-1-(imidazol-1-yl)-pent-4-in-2-ol2-(2,6-dichlorophenoxymethyl)-3,3-dimethyl-1-(imidazol-1-yl)-pent-4-in-2-ol2-(4-chlorophenoxymethyl)-3,3-dimethyl-1-(imidazol-1-yl)-5-iodo-pent-4-in-2-ol,2-(4-bromophenoxymethyl)-3,3-dimethyl-1-(imidazol-1-yl)-5-iodo-pent-4-in-2-olor2-(2,5-dichlorophenoxymethyl)-3,3-dimethyl-1-(imidazol-1-yl)-5-iodo-pent-4-in-2-ol,ora physiologically tolerated addition product thereof with an acid ormetal salt.